Light-sensitive silver halide photographic elements



June 17, 1952 W. D. BALDSIEFEN LIGHT-SENSITIVE SILVER HALIDEPHOTOGRAPHIC ELEMENTS Filed July 26, 1949 GELATIN SILVER HALIDECELLULOSE ACETATE BASE NON-HALATION DYE GELATIN AND No-p-TER.-OCTYL-PHENOXY ET OXY ETHYL SULFONATEv rra GELATIN AND Na.--TER-OCTYL-PHEOXY ETHxY ETHYL SULFONA GELATIN SILVER HALIDE CELLULOSEACETATE BASE GELATIN AND Nu- -TER-ocTYI.- PHENoxY ETHoxY ETHYL s LFoNATEi., GELATIN sILvER HAUDE m,4!'f cELLULosE AcETATE BASE GELATm SILVERHALIDE F G. 3.

wIlWlWWIllllI/B GELATIN SILVER HALIDE CONTAINING Nc1p-TER.OCTYLPHENOXYETHOXY ETHYL SULFONATE CELLULOSE FILM BASE GELATIN SILVER HALIDECELLULOSE ACETATE BASE NON-HALATION DYE, GELATIN, GLYOXAL ANNGpTER.OCTYL-PHENOXY ETHOXY ETHYL SULFONATE I IN1 LEYTOR. WALTER DEWEYALDs/EFEN A TTORNE Y Patented June 17, 1952 UNITED STATES Meur oFFIcELIGHT-SENSITIVE SILVER HALIDE PHOTO- GRAPHIC ELEMENTS ware Application.luly 26, 1949, Serial No. 106,962

(Cl.A 95-8) 6 Claims. 1

The invention relates to photographic elements, an outer Water-permeablelayer or stratum of which has improved surfacev characteristics. Moreparticularly','it relates to photographic films and paperswhich have anouter light-sensitive, anti-abrasion and/or non-halation layer" whichhas improved'surface characteristics and other usefulpro'perties. Italso relates to a process of coating vphotographic films and papers.

lhotographic films and papers are generally manufactured in the formofcontinuous sheets orv webs which are provided with various coatingsfrom predominantly aqueous "solutions The coatings are dried .byvpassing the coated web through a chamber maintained'at an elevatedtemperature. This is generally 'accomplished by festooning so that thelength of thev chamber can be kept'within reasonable limits.4 'Thecoatings which generally consist'of a Water-permeable oolloid whichserves as a binding agentfor the silver halides, anti-'hallation dyes orpigments, etc., are quite smooth and when the film or` paperis vagain"passed through the drying chamber With the coated surface'in contactWith the festoonin'gsupports, tend to slip with damage to the coatedsheet or web. Saponiu is generally used in the coating solutions in'order to facilitate the spreading of the coatings, but it is not alwaysuniform in properties and what is more serious Washes out duringphotographic processing operations which causes ."waterspots which arecaused by non-*wetting by Vsubsequent processing baths. Thesew'aterspots which are present in negative lms, etc., serious- 1y. aifect thequality of the resulting positive prints. Various surface active wettingagents have been proposed to facilitate spreading of gelatin silverhalide layers,"'antihalation layers and the like but they render thesurfaces smooth so'that slipping on the festooning supports becomes areal problem.V

An object of this invention is to improve the art ofY coating continuouslengths of photographic films and papers. A further object is'to providecoatings for photographic elements which have improved noni-Slipping"surface characteristics. A still further Yoltject'is to providephotographic elements with Water-permeable coatings Which have gooduniform rewetting characteristics. Still other objects will be apparentfrom the following' detailed description of the invention.

' It has been found that improved photographic films and papers can'bemade byincorporating in an outer water-permeable colloid light-sensitivesilver halide layer, a Water-permeable colloid anti-abrasion layer on awater-permeable backing or anti-halation layer or in a plurality of suchlayers a salt of an alkyl-substituted aryloxy alkylene ether sulfonateof the general formula:

i. where R is an alkyl radical of 4 to l2 carbon atoms, 'n is a cardinalnumber from 1 to 2 and M is an alkali metal or ammonium.`V R may bestraight chain or branched chanbutyl, amyl, hexyl, heptyl, octyl, nonylor decyl. The radical n is preferably 1 and R p-tertiary octyl.

- layer in question.

A coating solution for a non-halation backing layer was prepared bydissolving 400 grams of gelatin and 15 grams of nigrosine (Colour IndexNo. 865) in sufficient water to'make 10 liters. To this solution therewas added 5 grams of sodium p-tertiary-octyl phenoxy ethoxy ethylsulfonate of the'formulai (E Hg (IZIIS @appara-50-oHToHz-o-CHZ-onrsoNaom om This material Was then coated onto a cellulose acetate film baseVl las shwnin l'g'igl 1 `ofthe drawing to form non-'halation' layer 2`which was dried in the manner knownV to thea'rt. A'gelatino-silverhalide emulsion layer 3l 4was 'then coated from'an aqueous dispersionon'the bpposite surface of the support.` During` this latter operation nodifficulty was'encountered with the film slipping from the festooning"supports,V due to slipperiness of the` non-halation l'ais'fer'.'YExample II A gelatine-silver halide emulsion layer 5 was coated cinto aVcellulose acctate'iil'm base d" as Shown in Fig. 2 of the drawing anddr'jicl.n 'ro 10,000 grams of an anti-abrasion overcoating solutioncontaining 200 grainsof 'hard gelatin dissolved in 9,800 gramsv gfWater, there tvgsfdded 2 grams of sodium p-tertiary octylphenoxy ethoxyethyl sulfonate having the formula given in Example I and the resultingsolution was coated onto the silver halide emulsion layer to formantiabrasion layer 6 and dried. A sample of this material was thenexposed 'and processed in a developing bath containing 2 grams of metol,5 grams of hydroquinone, 100 grams of sodium sulfite and 6 grams ofborax dissolved in sufficient water to make a total volume of thesolution 1 liter. It Was observed that the material could be rapidlyplunged into the solution without the formation of air bubbles on theemulsion surface, and that the solution wet said surface completely,thus obviating the formation of Water-spots in the processed material.

Example III A continuous length of photographic fllm prepared as inExample II was coated on the back side with another gelatino-silverhalide emulsion layer, and passed through a drying chamber. This film isshown in Fig. 3 of the drawing and consists of cellulose acetate filmbase 4 which has superimposed on one surface gelatin silver halideemulsion layer 5 on which is superimposed gelatin layer 6 containingsodium p-tertiary, octyl phenoxy ethoxy ethyl sulfonate and on thereverse side of the film base is gelatin silver halide layer 1. Duringthis latter coating operation no difficulty was encountered because ofslippage of the material during its travel in festoons through thedrying.

Example IV To 10,000 grams of a gelatino-silver halide emulsioncontaining approximately 1600 grams of solids there was added 8 grams ofsodium p-tertiary octylphenoxyethoxyethyl sulfonate having the formulaset forth in Example I; the emulsion Was then coated on a cellulose filmbase 8 as shown in Fig. 4 of the drawing in the manner known in the artto form layer 9. It was observed that the emulsion coated smoothly andwith uniform adherence to the base. It was found that the emulsionsurface was wetted instantly during the processing operations, and thatno spots were visible when the processed lm was finally dried.

Emample V A continuous length of cellulose acetate lm base 2 as shown inFig. 5 of the drawing was coated on its back surface with an aqueoussolution made by dissolving 400 grams of gelatin, grams of nigrosin insufiiciet water to make 10 liters of solution. To this solution therewas added 1.2 grams of glyoxal and 5 grams of sodiump-tertiary-octyl-phenoxy ethoxy ethyl sulfonate having the formula setforth in Example I and resulting layer I was dried in a tunnel providedwith festooning supports. The front surface of the lm base was thencoated with a sliver iodo bromide emulsion layer 3 from asolution of thetype described in Example II and dried in like manner. The film had theadvantage that the surfaces did not slip on the festooning supports. Inaddition, the sodium p-tertiary octylphenoxy ethoxy ethyl sulfonate didnot wash out during processing and resulted in negative pictures whichwere free from water spots. The glyoxal, moreover, preventedreticulation of layer I' during processing.

The above coatings were made under conditions that no actinic lightexposed the light-sensitive silver halide coatings.

,4 In place of the specific anti-halation dye of the foregoing examplesthere may be substituted one or more other dyes or pigments or colloidalsilver. The particular dye or dyes, etc., used depends on thecharacteristics of the emulsion. The anti-halation material should beabsorptive of light of wavelengths to which the emulsion is sensitive.Suitable additional dyes include:

Auramine (C. I. 655) Helianthin (C. I. 142, 146) Brilliant yellow S (C.I'. 144) Chrysoin (C. I. 148) Acid blue black (C. I. 246) Rhodamine (C.I. 749, '750, '751, '146, 753, 761, r163) Fuchsin (C. I. 677) SafranineG (C. I. 841) Ponceau 6R (186) Crocein scarlet (C. I. 277, 251, 286,252, 291, 183) Azorubin (C. I. 179) Safranine O (C. I. 841) Ponceau 2R(C. I. 79)

Spirit soluble nigrosine (C. I. 864) Metanil yellow (C. I. 138) Acidmagenta O (C. I. 692) The C. I. numbers in the foregoing table refer toColour Index numbers, the Colour Index being the Society of Dyers andColourists Colour Index, edited by F. M. Rowe, published by the society,Bradford, Yorkshire, England.

Similarly in place of gelatin as the waterpermeable colloid other suchmaterials may be used. Among such materials are albumin, casein, agaragar, polyvinyl alcohol, hydrolyzed ethylene/vinyl acetate copolymers,polydioxolanes, etc.

The, invention is not limited to the use of cellulose acetate film baseas stated above, but can be used with practically any type oftransparent film or paper e. g., baryta or resin coated paper; or filmcomposed of polyamides, cellulose nitrate, polyvinyl acetals, cellulosepropionate, cellulose mixed esters, cellulose ethers, vinyl chloride andcopolymers, styrene, acrylonitrile and copolymers, polyesters, vinylacetate and copolymers, vinyl fluoride and copolymers, polyvinylalcohol; transparentized paper, etc.

Sensitizing dyes and other emulsion adjuvants may be added to the aboveemulsion layers without their function being affected by the alkylsubstituted aryloxy alkylene ether sulfonates. This is particularlyadvantageous in the case of the so-called duplicoated photographicelements, where an emulsion layer may be sensitized to one portion ofthe spectrum, while the emulsion layer on the opposite side of a filmbase may be sensitized to another portion of the spectrum, or may not beespeciallysensitized at all. The agents of Formula I are included in atleast one, and preferably both of the emulsion layers, to facilitatecoating and subsequent processing. The principal advantage of theinvention, however, is that it allows the manufacture of such a doublecoated element, without the danger of waste caused by the elementslipping off from the festooning supports on to the floor of the dryingtunnels.

A further advantage over saponin is that uniform results can beobtained. The former being a naturally occurring material often variesin properties.

As many Widely different embodiments of this invention can be madewithout departing from the spirit and scope thereof, it is to beunderstood that the invention is not to be limited except as defined bythe claims.

What is claimed is:

1. A photographic element comprising a support and a light-sensitivesilver halide emulsion layer said element having at least onewaterpermeable outer layer which contains a small amount of a compoundof the formula:

3. A photographic element comprising a transparent flexible lm basebearing a light-sensitive colloid silver halide emulsion layer, awaterpermeable colloid anti-abrasion layer on said emulsion layer and alayer of a water-permeable colloid containing an anti-halation materialon the reverse surface of the base at least one of the latter two layerscontaining a small amount of a compound of the formula:

Q (o-om-cHm-o-oHz-CHZ-som wherein R is an alkyl radical of 4 to 12carbon atoms. n is a cardinal number from 1 to 2 and M is a member takenfrom the group consisting of alkali metals and ammonium.

4. A photographic element comprising a transparent exible film basebearing a light-sensitive colloid silver halide emulsion layer, awaterpermeable colloid anti-abrasion layer on said emulsion layer and alayer of a water-permeable colloid containing an anti-halation materialon the reverse surface of the base at least one of the latter two layerscontaining a small amount of a compound of the formula:

CH; CH: CHV-CHT- O-CHg-CHz-O-CHVCHz-SOaNa OH: Ha

5. A photographic element comprising a transparent flexible film basebearing a gelatino silver iodo bromide emulsion layer on one surface, agelatin anti-abrasion layer on said emulsion layer and a layer ofgelatin containing an anti-halation material on the reverse surface ofthe base each of the two latter layers containing a small amount of acompound of the formula:

and a small amount of glyoxal.

6. An element as set forth in claim 5 wherein the anti-halation materialis acid Magenta O.

WALTER DEWEY BALDSIEFEN.

REFERENCES CITED The following references are of record in the le ofthis patent:

UNITED STATES PATENTS Number Name Date 1,946,635 Murray et a1 Feb. 13,1934 2,115,192 Bruson Apr. 26, 1938 2,118,059 Slack et al. May 24, 19382,143,759 Bruson Jan. 10, 1939 2,287,807 Kendall June 30, 1942 2,400,532Blake May 21, 1946

1. A PHOTOGRAPHIC ELEMENT COMPRISING A SUPPORT AND A LIGHT-SENSITIVESILVER HALIDE EMULSION LAYER SAID ELEMENT HAVING AT LEAST ONEWATERPERMEABLE OUTER LAYER WHICH CONTAINS A SMALL AMOUNT OF A COMPOUNDOF THE FORMULA: